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For Batman the big ones (other than DKR) are Year One, The Killing Joke, and The Long Halloween. And if you like The Long Halloween, its sequel Dark Victory is good as well. I like the Batman: Earth One graphic novels, but it's kind of a reimagined take on Batman, and sometimes people have a problem with that.
Superman: Earth One is good as well, but if I was going to recommend a Superman comic it'd be All Star Superman. It's probably the best Superman comic ever, but don't go in expecting gritty realism. Which isn't to say it doesn't take itself seriously. It embraces the 1950s insanity of Superman and makes it work.
Marvel's a little tougher, because they don't have the obvious self-contained stories to recommend like DC does. Recommending things from Marvel you start getting into entire runs, which is basically saying "get this series of 8 graphic novels".
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